Apparatus and techniques to treat substrates using directional plasma and point of use chemistry

ABSTRACT

In one embodiment, an apparatus to treat a substrate may include an extraction plate to extract a plasma beam from a plasma chamber and direct the plasma beam to the substrate. The plasma beam may comprise ions forming a non-zero angle of incidence with respect to a perpendicular to a plane of the substrate; and a gas outlet system disposed outside the plasma chamber, the gas outlet system coupled to a gas source and arranged to deliver to the substrate a reactive gas received from the gas source, wherein the reactive gas does not pass through the plasma chamber.

FIELD

The present embodiments relate to electronic device processingtechniques, and more particularly, to processing for treating thesurface of a substrate.

BACKGROUND

As integrated devices continue to scale to smaller dimensions, theability to pattern features becomes increasingly difficult. Thesedifficulties include in one aspect the ability to etch features topreserve or transfer a pattern into a substrate. In many deviceapplications a patterned feature may include a metal layer that isdifficult to etch because the metal does not readily form volatile etchproducts using known reactive ion etching or similar processes. Etchingof metal layers via physical sputtering may be problematic because ofthe tendency for sputtered species of a given metal layer to redepositon unwanted surfaces of the substrate including on surfaces of devicefeatures being formed. This may lead to patterned structures such aspillars or lines having non-vertical sidewalls, as well as havingexcessive material redeposited from etching of a non-volatile metalunderlayer.

With respect to these and other considerations the present improvementsmay be useful.

SUMMARY

This Summary is provided to introduce a selection of concepts in asimplified form further described below in the Detailed Description.This Summary is not intended to identify key features or essentialfeatures of the claimed subject matter, nor is the summary intended asan aid in determining the scope of the claimed subject matter.

In one embodiment, an apparatus to treat a substrate may include anextraction plate to extract a plasma beam from a plasma chamber anddirect the plasma beam to the substrate, the plasma beam comprising ionsforming a non-zero angle of incidence with respect to a perpendicular toa plane of the substrate; and a gas outlet system disposed outside theplasma chamber, the gas outlet system coupled to a gas source andarranged to deliver to the substrate a reactive gas received from thegas source, wherein the reactive gas does not pass through the plasmachamber.

In another embodiment, a system to treat a substrate may include aplasma chamber to house a plasma; an extraction plate to extract aplasma beam from the plasma chamber and direct the plasma beam to thesubstrate, the plasma beam comprising ions forming a non-zero angle ofincidence with respect to a perpendicular to a plane of the substrate;and a gas outlet system disposed outside the plasma chamber, the gasoutlet system coupled to a gas source and arranged to deliver to thesubstrate a reactive gas received from the gas source, wherein thereactive gas does not pass through the plasma chamber.

In another embodiment, a method of treating a substrate may includeextracting a plasma beam from a plasma, wherein the plasma beamcomprises ions forming a non-zero angle of incidence with respect to aperpendicular to a plane of the substrate; and directing a reactive gasfrom a gas source to the substrate, wherein the reactive gas does notpass through the plasma.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A depicts a system according to embodiments of the disclosure;

FIG. 1B depicts one embodiment of the system of FIG. 1A;

FIG. 1C depicts a plan-view of the embodiment of an apparatus of FIG.1B;

FIG. 1D depicts details of geometry of a processing apparatus andsubstrate according to various embodiments;

FIG. 2A through FIG. 2D depict an example of substrate etching accordingto embodiments of the disclosure;

FIG. 3A and FIG. 3B provide results showing the effect of employingpoint-of-use chemistry during etching of a pillar; and

FIG. 4 depicts an exemplary process flow.

DETAILED DESCRIPTION

The present embodiments will now be described more fully hereinafterwith reference to the accompanying drawings, where some embodiments areshown. The subject matter of the present disclosure may be embodied inmany different forms and are not to be construed as limited to theembodiments set forth herein. These embodiments are provided so thisdisclosure will be thorough and complete, and will fully convey thescope of the subject matter to those skilled in the art. In thedrawings, like numbers refer to like elements throughout.

This present embodiments provide novel apparatus and novel techniques totreat substrates and in particular novel apparatus and techniques totreat a substrate surface, such as to etch a surface feature. As usedherein the term “substrate” may refer to an entity such as asemiconductor wafer, insulating wafer, ceramic, as well as any layers orstructures disposed thereon. As such, a surface feature, layer, seriesof layers, or other entity may be deemed to be disposed on a substrate,where the substrate may represent a combination of structures, such as asilicon wafer, oxide layer, metal layer, and so forth.

In various embodiments, apparatus are disclosed that provide ion beam(or “plasma beam”) treatment of a substrate as well as reactive gastreatment of the substrate. The ion beam and reactive gas may beprovided in a configuration and manner that delivers point-of-usereactive chemistry to a surface of a substrate being treated, such as asubstrate being etched.

FIG. 1A depicts a system 100 according to embodiments of the disclosure.The system 100 includes a hybrid processing apparatus, shown incross-section as the apparatus 102. FIG. 1B depicts one embodiment ofthe system 100 including a perspective view of an embodiment of theapparatus 102. FIG. 1C depicts a plan-view of the embodiment ofapparatus 102 of FIG. 1B, while FIG. 1D depicts details of geometry ofan apparatus 102 and substrate according to various embodiments. Asdetailed in FIG. 1A, the system 100 may include a plasma chamber 104 tohouse a plasma 106. In some embodiment, the plasma chamber 104 may beoperated at pressures between 1 mTorr and 300 mTorr. The embodiments arenot limited in this context. As shown in FIG. 1A, the plasma chamber 104is disposed adjacent a processing chamber 101, where a lower pressurebelow 10⁻⁵ Torr may be maintained by a vacuum pumping system comprisedof known pumping apparatus, such as a turbomolecular drag pumps backedby rotary pumps. Gaseous plasma precursor may be fed into the plasmachamber 104 from a gas manifold 122 through a plasma gas line 125. Invarious embodiments, inert gases (He, Ne Ar, Kr, Xe) or mixtures ofinert gases with reactive gases such as H₂, NF₃, C₁₂, Br₂ C_(x)F_(y)etc.) may be used as plasma precursors, where inert gas ions may form inaddition to reactive gas ions in the plasma chamber 104. The plasma 106may be generated by coupling electric power from a power generator 108to the rarefied gas in the plasma chamber 104 through an adequate plasmaexciter. In the followings the generic term “plasma source” includes thepower generator, the plasma exciter, the plasma chamber, and the plasmaitself. The plasma source may be an, inductively-coupled plasma (ICP)source, toroidal coupled plasma source (TCP), capacitively coupledplasma (CCP) source, helicon source, electron cyclotron resonance (ECR)source, indirectly heated cathode (IHC) source, glow discharge source,or other plasma sources known to those skilled in the art. Therefore,depending on the nature of the plasma source the power generator 108 maybe an rf generator, a dc power supply, or a microwave generator, whileplasma exciter may include rf antenna, ferrite coupler, plates,heated/cold cathodes, helicon antenna, or microwave launchers. Thesystem 100 further includes a bias power supply 110 connected to theplasma chamber 104 or to a substrate holder 118. Extraction of an plasmabeam 114 comprising positive ions through the extraction plate 112 mayaccomplished by either elevating the plasma chamber 104 at positivepotential and grounding the substrate holder 118 or by grounding theplasma chamber 104 and applying negative potential on the substrateholder 118. The bias power supply 110 may operate in either a dc mode orpulsed mode having a variable duty cycle, or an AC mode. The extractionplate 112 may be arranged generally according to known design to extractions in the plasma beam 114 in a manner that allows control of the ionangular distribution, i.e., the angle of incidence of the plasma beam114 with respect to a substrate 116 and the angular spread as detailedbelow.

The apparatus 102 also includes a reactive gas outlet assembly, shown asgas outlet assembly 120, where the gas outlet assembly 120 is capable ofdelivering a reactive gas 128 to the substrate 116. The gas outletassembly 120 is coupled to the gas manifold 122 an may include aplurality of gas outlets. The gas manifold 122 may include a source ofthe reactive gas 128 in liquid or gaseous form in addition to the gasprecursor for the plasma 106, as discussed above. The gas manifold 122in some embodiments may include more than one source of reactive gas,and more than one source of plasma gaseous precursor where the differentsources contain different gases. The gas manifold 122 may be coupled tothe gas outlet assembly 120 via one gas line or over a plurality of gaslines. In the example of FIGS. 1A and 1B, the reactive gas source 122 iscoupled to a gas line 124 and a gas line 126, where the different gaslines enter the gas outlet assembly 120 at different portions of theapparatus 102.

The system 100 further includes a control system 132. The control system132 may be coupled to various components of system 100 including biaspower supply 110, plasma power supply 108, and gas manifold 122. Thecontrol system 132 may be arranged to vary at least one system parameterof system 100. Examples of a system parameter include level of RF powerapplied to the plasma chamber 104, RF waveform, extraction voltage ofthe ion beam applied by the bias power supply 110, the duty cycle andfrequency of the pulsed bias voltage, or z spacing between substrate 116and extraction plate 112, meaning the spacing along the Z-axis betweensubstrate 116 and extraction plate 112. The configuration of theextraction plate 112 is another example of a system parameter and mayinclude the shape or size of apertures in the extraction plate, and soforth. At least one of these system parameters may be varied from afirst value to a second value, wherein the plasma beam 114 has a firstshape at the first value and a second shape at the second value. In thismanner parameters of the plasma beam 114 such as angle of incidence onthe substrate, angular spread (ranges of angles of incidence), and soforth, may be controlled. This allows the plasma beam 114 to be directedto a substrate according to an application. For example, when thesubstrate 116 includes patterned features (not shown in FIG. 1A),vertical surfaces of a patterned feature may be better treated bydirecting the plasma beam 114 at a first angle of incidence, whilehorizontal surfaces may be better treated by directing the plasma beam114 at a second angle of incidence.

Turning now to FIG. 1B in particular there is shown one embodiment ofthe gas outlet assembly 120 where a plurality of gas orifices 142 areprovided, extending along top and bottom sides of the extractionaperture 140 of extraction plate 112. Because the reactive gas 128 ischanneled from the gas manifold 122 to gas outlet assembly 120 while notpassing through the plasma chamber 104, in various embodiments thereactive gas 128 may be directed to impinge on the substrate 116 whilenot being ionized, or otherwise excited. In this manner a neutralreactive gas may be provided to the substrate. In addition, the reactivegas may remain in a non-dissociated state (or intact state) whenimpinging on the substrate. The ability to provide such “point of usechemistry” where reactive gas may be provided directly to a substrateallows in some instances an unionized, non-dissociated, and unexcitedgas species to contact the substrate. In other instances dissociation,radical generation, excitation, or ionization may take place whenconditions such as gas flow rate, gas pressure proximate the substrate116, or other factors are adjusted to increase interaction with plasmabeam 114.

While the plasma beam 114 may be spatially confined according to thesize of the extraction aperture 140 and the voltage differenceestablished between the substrate 116 and plasma 106, the reactive gas128 may spread out after exiting the gas outlet assembly 120. Asdetailed below, in regions where the ions of plasma beam 114 andreactive gas 128 overlap on the substrate 116, etching of the substrate116 may take place.

In various embodiments as illustrated in FIG. 1B and FIG. 1C, theextraction aperture 140 may have an elongated shape. For example, asshown in FIG. 1C, the extraction aperture 140 may have an aperture widthW along a first direction parallel to the X-axis in the Cartesiancoordinate system shown. The extraction aperture 140 may have anaperture length along a second direction perpendicular to the firstdirection, in other words, along the Y-axis, wherein the aperture widthW is greater than the aperture length L. This may generate the plasmabeam 114 as a ribbon beam. In some examples W may have a value in therange of 150 mm to 300 mm or greater, while L has a value of 3 mm to 30mm

In order to treat a substrate 116 in its entirety, the substrate holder118 may scan the substrate along the direction 117 parallel to theY-axis, for example. Turning also to FIG. 1D, in various embodiments,the plasma beam 114 may be parallel, convergent, or divergent, and mayprovide ions having broad angular distributions (trajectoriesdistributed over a wide range of angles of incidence around mean angleof incidence), such as 30 degrees or greater, or ions may have a narrowangular distribution (trajectories distributed over a narrow range ofangles of incidence), such as less than 5 degrees. The ions may form anon-zero angle of incidence, shown as θ, with respect to a perpendicular150 to a plane 152 of the substrate 116, where the plane 152 may lieparallel to the X-Y plane. The distribution of angles of incidence maybe characterized by a monomodal distribution or a bimodal distributionin different embodiments. As shown in FIG. 1D a given distribution ofangles of incidence for plasma beam 114 may be determined by the shapeof a plasma sheath boundary 154 of the plasma 106. In particular, ameniscus 156 may form in the extraction aperture 140 from which ions ofthe plasma beam 114 are extracted. The shape of the meniscus 156 may beadjusted by varying parameters such as plasma density (for example, RFpower and/or gas pressure in the plasma chamber) extraction voltageapplied between plasma chamber 104 and substrate 116, or the extractionplate-substrate holder gap length. In some embodiments, a beam blocker(not shown) may be provided within plasma chamber 104 adjacent theextraction aperture 140 to define two separate plasma beams that areextracted through the extraction aperture 140. In the above manner theangle(s) of incidence of ions of the plasma beam 114 may be controlled.

FIG. 2A through FIG. 2C depict an example of substrate etching using aplasma beam in conjunction with point-of-use reactive chemistryaccording to embodiments of the disclosure. In FIG. 2A there is shown adevice structure 202 that includes a base layer 204, and metal layer206. The base layer 204 may represent more than one layer including asemiconductor wafer, or magnetic storage substrates, as well as otherlayers. In various embodiments the metal layer 206 may be a metallicmaterial or mixture of metallic material that is resistant to etching byreactive ion etching processes. Examples of such metals include Cu, Ta,Pt, Ru, and other non-volatile metals. In some embodiments a combinationof metals such as Pt, Ru, and Ta may be employed in a stack of layersused to form a memory device such as a magnetic random access memory(MRAM).

In order to etch the metal layer 206, to form a feature containing aportion of the metal layer 206, a mask feature may be provided. In oneexample, the stack 208 may be a mask layer to be removed later, such asa hard mask. In other examples, the stack 208 may include multiplelayers including device layers to remain as part of a final device. Inthese different examples, the stack 208 may act as a mask defining anexposed region 206A and a protected region 206B. In the approach shownin FIG. 2A, a reactive gas 210 may be used in conjunction with a plasmabeam to etch the metal layer 206. In some embodiments the reactive gas210 may be provided from a gaseous source while in other embodiments thereactive gas 210 may be provided from a liquid source. While not shownin FIG. 2A, ions may be provided simultaneously to the substrate 200together with reactive gas 210. In some embodiments, the reactive gasmay be provided to the substrate 200 in an apparatus such as apparatus102, in conjunction with a plasma beam that directs ions to thesubstrate 200.

In various embodiments, the reactive gas 210 may be provided to thesurface of a substrate 200, wherein the reactive gas 210 is an adsorbingspecies that condenses to form an adsorbed layer or layers on surfacespresented by the substrate 200. As illustrated in FIG. 2A, the reactivegas may form a conformal coating, shown as the coating 216, in thisexample being a conformal adsorbed coating. In particular, the coating216 is disposed on the surface 220 of the metal layer 206, as well as onthe sidewall 218 of the stack 208. In some embodiments, the reactive gas210 may comprise an organic molecule, and in particular embodiments, thereactive gas 210 may comprise a polar molecule. Examples of moleculessuitable for reactive gas 210 include methanol (CH₃—OH), ethanol(CH₃—CH₂—OH), isopropanol (CH₃—CHOH—CH₃), dimethilether (CH₃—O—CH₃), oracetone (CH₃—CO—CH₃), or other reactants. The embodiments are notlimited in this context. In some cases the reactive gas 210 may bedeposited uniformly over substrate surfaces and may coat threedimensional structures in a uniform manner to form the coating 216.

Turning now to FIG. 2B there is shown a further scenario for etching themetal layer 206. In this example, an ion 212, shown as a positive ion,is directed to the substrate 200. The ion 212 may represent a pluralityof ions directed in a plasma beam as shown, for example, at FIG. 1A. Theion 212 may form a non-zero angle of incidence with respect to theperpendicular 150, as shown. In other words, the trajectory of ion 212may not be parallel to the sidewall 218, wherein the ion 212, or a groupof ions having similar trajectories, may impinge upon the sidewall 212as well as the surface 220. In the scenario of FIG. 2B, the ion 212 maypenetrate through the coating 216, and strike the metal layer 206,causing a metal species 214 such as a metal atom to be sputter-ejected(sputter etched) from the metal layer 206. This process may happenrepeatedly, causing metal to be etched from exposed region 206A. Asfurther shown in FIG. 2B, the sputtered metal, such as metal species214, may react with the reactive gas 210, including reactive gasadsorbed on the metal layer 206 in coating 216 or in the vicinity of themetal layer 206. In this manner a volatile etch product 224 may begenerated containing material from the reactive gas 210 and metalspecies 214. The volatile etch product 224 may enter the gas phase asshown, and may be transported away from the substrate 200.

In order to prevent the sputtered metal species from redepositing inunwanted areas such as the sidewall 218, the coating 216 may bereplenished by condensing species of the reactive gas 210. The reactivegas may form a coating of sub-nanometer thickness, providing anunfavorable surface for redisposition of etched species, such as metalatoms or volatile etch product 224. Accordingly, the metal layer 206 maybe removed by a combination of sputtering and reaction with a reactivegas 210, where the reactive gas is provided in an adsorbed coating on asurface of the metal layer 206. Moreover, the reactive gas 210 maycondense in a coating 216, where the coating 216 inhibits redispositionof etched metal-containing material.

Turning now to FIG. 2C there is shown a later instance after theprocesses of FIGS. 2A and 2B have etched the metal layer 206 in theexposed region 206A. In this example, the exposed region 206A has beencompletely removed, generating the patterned feature 206C of the metallayer 206. As shown, the patterned feature 206C, as well as the stack208, may have a vertical sidewall for sidewall 218, meaning the sidewall218 extends parallel to the Z-axis. In addition, the sidewall 218 may befree of redeposited etch product, where the etch product may be thevolatile etch product 224 or other material removed from the metal layer206. The generation of a vertical sidewall free of etch product mayresult from a combination of the formation of the coating 216 as well asthe directionality of the ions provided during etching, such as ion 212.By providing ions at a non-zero angle with respect to the perpendicular150, where the non-zero angle may be tuned by a control system 132, forexample, ions may be directed to the appropriate surfaces at appropriateangles of incidence to ensure that a vertical sidewall profile of thestack 208, as well as patterned feature 206C is maintained.

In some embodiments the process shown in FIGS. 2A to 2C may be performedmultiple times to etch a layer stack containing multiple non-volatilemetal layers. For example, a layer stack in an MRAM memory cell mayinclude multiple layers including multiple magnetic layers, MgO layer,as well as multiple contact layers, where the contact layers may becomposed of Ta, Pt, Fe, Co, Ru, Ti, or other non-volatile metal.

Accordingly, the process of FIGS. 2A to 2C may be used to etch themultiple contact layers. FIG. 2D illustrates an example of a devicestructure 240 obtained after etching using point-of-use reactivechemistry according to embodiments of the present disclosure. The devicestructure 240 includes a plurality of pillar structures, shown as pillarstructures 242, where the pillar structures are formed by etching alayer stack 234. Within the layer stack 234 there are shown multiplelayers including a layer 232 and a layer 236, where the layer 232 aswell as layer 236 are non-volatile metals. The layer 232 and layer 236may be subject to the treatment shown in FIGS. 2A to 2C so etching takesplace while avoiding redeposition upon sidewalls 238. Accordingly thepillar structures 242 may have vertical profiles, meaning the sidewallslie parallel to Z-axis. Additionally, the sidewalls 218 may be free ofredeposited metal formed when the layer 232 and layer 236 are etched.

In some embodiments, the etching of layer 232 and layer 236 may beperformed by an apparatus such as apparatus 102. In examples, where thepillar structures 242 are part of a memory device, the memory device maybe formed in a silicon wafer or other substrate that includes many diehaving an array of pillars forming a memory device. The etching shown inFIGS. 2A to 2C may be performed across a given substrate such as asilicon wafer by scanning the substrate with respect to an extractionaperture 140. In some embodiments, etching may be performed by scanninga substrate back and forth over a plurality of scans to complete etchingof a given layer or stack of layers. In particular embodiments, reactivegas may be provided to a substrate during an entire etch process whileions are directed to a substrate. In other embodiments, the reactive gasmay be applied intermittently, such as during one scan out of 10 scansof a substrate.

In some embodiments substrate temperature of a substrate such assubstrate 116 may be maintained within a target temperature range toensure coverage of substrate structures by a condensed layer of thereactive gas is maintained during etching. This target temperature rangemay be tuned according to the molecule being used for the reactive gas,for example. In various embodiments, the target temperature range mayspan −60° C. to +400° C.

FIG. 3A and FIG. 3B provide results showing the effect of employingpoint-of-use chemistry during etching on the resulting structure of apillar device. In FIG. 3A there is shown an electron micrograph of apillar structure 304 formed by etching a stack including a non-volatilemetal layer, where the non-volatile metal layer is etched using argonions. The pillar structure 304 includes a central portion 306, and asidewall deposit 312 on sidewall 310 having a width of 10 nm. In FIG. 3Bthere is shown an electron micrograph of a pillar structure 314 formedby etching a stack including a non-volatile metal layer, where thenon-volatile metal layer is etched by providing methanol gas in additionto argon ions during etching. The pillar structure 314 includes inaddition to central portion 306, and does not include a sidewall depositon sidewall 310. Accordingly, redeposition of material along sidewallsis removed in this example by providing methanol directly to a substratewhile etching with angled argon ion beams. Notably, redeposition may becontrolled by adjusting factors including substrate temperature, amountof methanol provided to the substrate, angle of incidence of ions, amongother factors. In some experiments, MRAM arrays having pitch as small as130 nm were subject to electrical and magnetic measurements. Whenprocessed according to the present embodiments using an etch mixturesuch as methanol and argon ion mixture, where the methanol is applied tothe substrate while not passing through a plasma chamber, the arrayshave exhibited 98-100% yield. This yield indicates little or no yieldloss due to sidewall metal redeposition.

While the aforementioned embodiments emphasize the delivery of anon-dissociated gas and also unexcited reactive gas to a substrate, insome embodiments a fraction of reactive gas molecules may be excited, orionized, or partially or fully dissociated before impinging upon asubstrate. The fraction of such species may be tuned to promotereactivity while maintaining a layer or coating of condensed gas speciesto inhibit redeposition of etch products on sidewalls.

FIG. 4 depicts an exemplary process flow 400. At block 402, theoperation is performed of extracting a plasma beam from a plasma,wherein the plasma beam comprises ions forming a non-zero angle ofincidence with respect to a perpendicular to a plane of a substrate. Insome embodiments, the plasma beam may be extracted through an extractionaperture having an aperture width along a first direction and anaperture length along a second direction perpendicular to the firstdirection, wherein the aperture width is greater than the aperturelength, wherein the plasma beam is a ribbon beam.

At block 404, the operation is performed of directing a reactive gasfrom a gas source to the substrate, wherein the reactive gas does notpass through the plasma. In some examples, the reactive gas may beprovided through a gas outlet system that provides reactive gas to thesubstrate, where the reactive gas remains in a neutral state andundecomposed when impinging upon the substrate.

The present embodiments provide various advantages over conventionalprocessing to define features in a substrate. One advantage lies in theability to perform etching of non-volatile metals to form patternedfeatures while avoiding or reducing redeposition of etched material onpatterned features. Another advantage is the ability to independentlydeliver sputtering ions and reactive gas to a substrate to provideindependent tuning of sputtering ions and reactive gas during etching.

The present disclosure is not to be limited in scope by the specificembodiments described herein. Indeed, other various embodiments of andmodifications to the present disclosure, in addition to those describedherein, will be apparent to those of ordinary skill in the art from theforegoing description and accompanying drawings. Thus, such otherembodiments and modifications are in the tended to fall within the scopeof the present disclosure. Furthermore, the present disclosure has beendescribed herein in the context of a particular implementation in aparticular environment for a particular purpose, while those of ordinaryskill in the art will recognize the usefulness is not limited theretoand the present disclosure may be beneficially implemented in any numberof environments for any number of purposes. Thus, the claims set forthbelow are to be construed in view of the full breadth and spirit of thepresent disclosure as described herein.

What is claimed is:
 1. An apparatus to treat a substrate, comprising: anextraction plate to extract a plasma beam from a plasma chamber anddirect the plasma beam to the substrate, the plasma beam comprising ionsforming a non-zero angle of incidence with respect to a perpendicular toa plane of the substrate; and a gas outlet system disposed outside theplasma chamber, the gas outlet system coupled to a gas source andarranged to deliver to the substrate a reactive gas received from thegas source, wherein the reactive gas does not pass through the plasmachamber, and wherein the gas outlet system comprises a channel, thechannel extending along an edge of the plasma chamber.
 2. The apparatusof claim 1, wherein the channel terminates at the extraction plate, andwherein the gas outlet system is arranged to deliver the reactive gas tothe substrate alongside the plasma beam.
 3. The apparatus of claim 1,wherein the extraction plate comprises an extraction aperture having anaperture width along a first direction and an aperture length along asecond direction perpendicular to the first direction, wherein theaperture width is greater than the aperture length, wherein the plasmabeam is a ribbon beam, wherein the gas outlet system comprises aplurality of gas orifices, wherein the plurality of gas orifices arearranged along a side of the extraction aperture along the firstdirection, and wherein at least one orifice of the plurality of orificesis coupled to the channel.
 4. The apparatus of claim 1, wherein thereactive gas comprises a non-dissociated gas.
 5. The apparatus of claim1, wherein the reactive gas comprises methanol, ethanol, acetone, orother polar molecule.
 6. The apparatus of claim 1, wherein the gasoutlet system comprises a first set of outlets and a second set ofoutlets, wherein the gas source is coupled to the first set of outlets,the apparatus further comprising a second gas source, the second gassource coupled to the second set of outlets and configured to deliver asecond reactive gas to the substrate.
 7. A system to treat a substrate,comprising: a plasma chamber to house a plasma; an extraction plate toextract a plasma beam from the plasma chamber and direct the plasma beamto the substrate, the plasma beam comprising ions forming a non-zeroangle of incidence with respect to a perpendicular to a plane of thesubstrate; and a gas outlet system disposed outside the plasma chamber,the gas outlet system coupled to a gas source and arranged to deliver tothe substrate a reactive gas received from the gas source, wherein thereactive gas does not pass through the plasma chamber, and wherein thegas outlet system comprises a channel, the channel extending along anedge of the plasma chamber.
 8. The system of claim 7, wherein theextraction plate comprises an extraction aperture having an aperturewidth along a first direction and an aperture length along a seconddirection perpendicular to the first direction, wherein the aperturewidth is greater than the aperture length, wherein the plasma beam is aribbon beam, the system further comprising a substrate holder configuredto scan the substrate along the second direction.
 9. The system of claim8, wherein the gas outlet system comprises a plurality of gas orifices,wherein the plurality of gas orifices are arranged along a side of theextraction aperture along the first direction, and wherein at least oneorifice of the plurality of orifices is coupled to the channel.
 10. Thesystem of claim 7 further comprising a control system to vary at leastone system parameter from a first value to a second value, wherein theplasma beam has a first shape at the first value and a second shape atthe second value, and wherein the at least one system parametercomprises: level of RF power applied to the plasma chamber, RF waveform,extraction voltage of the plasma beam, configuration of extractionplate, or spacing between substrate and extraction plate.
 11. The systemof claim 7, wherein the reactive gas comprises a polar molecule, andwherein the plasma beam comprises inert gas ions.